Thio-substituted(2.2.1)bicyclic compounds as antifoggants for silver halide emulsions

ABSTRACT

PHOTOGRAPHIC COMPOSITIONS CONTAINING THIO-SUBSTITUTED POLYCYCLIC COMPOUNDS. IN ONE ASPECT, THE THIO-SUBSTITUTED COMPOUNDS CONTAINING A THIO-SUBSTITUTED (2.2.1) BICYCLIC MOIETY ARE GOOD ANTIFOGGANTS IN PHOTOGRAPHIC SILVER HALIDE COMPOSITIONS.

United States Patent ABSTRACT OF THE DISCLOSURE Photographic compositions containing thio-substituted polycyclic compounds. In one aspect, the thio-substituted compounds containing a thio-substituted [2.2.1] bicyclic moiety are good antifoggants in photographic silver halide compositions.

This invention relates to photographic compositions and in particular to photographic compositions containing certain thio-substituted polycyclic compounds. In one aspect, this invention relates to photographic compositions containing thio-substituted polycyclic compounds which provide improved antifoggant or stabilizing properties in said compositions. In another aspect, this invention relates to silver halide photographic compositions having a very useful combination of ingredients.

It is known that sulfur compounds such as mercaptans and simple thioethers can be used to sensitize silver halide emulsions, providing improved photographic speed such as, for example, in Dann and Chechak, US. Pat. 3,046,134 issued July 24, 1962. Various sulfur-containing and nitrogen-containing compounds have also been used as antifoggants in silver halide emulsions as disclosed in Glafkides, Photographic Chemistry, 1958, pp. 374 378, However, improved additives to silver halide compositions which provide increased stability, improved antifogging of the emulsion, improved speed and the like or combinations of these properties without adversely affecting others are desirable.

We have now found new photographic composition combinations which exhibit improved photographic properties and provide an improved image record. Generally, we have found that light-sensitive, photographic compositions used in combination with a thio-substituted polycyclic compound containing the moiety:

provide improved photographic properties, especially such improved properties as reduced fog and improved stability of the element. This improvement is quite unexpected since the thio substitution adjacent a [2.2.1] bridged ring would be expected to be quite inactive and inert.

"One preferred embodiment of our invention relates to photographic compositions comprising compounds having a thio-substituted [2.2.1] bridged-ring moiety. Compounds containing this moiety can be macrocyclic compounds, but are preferably simple compounds containing at least one such moiety or polymeric compounds which contain recurring units wherein at least one of the recurring units contains this moiety.

In another preferred embodiment, the bridged ring is a divalent bridged Diels-Alder adduct of cyclopentadiene and a dieneophile.

Another preferred embodiment of this invention relates to photographic silver halide compositions comprising a thio substituted [2.2.1] bicyclic compound.

In another preferred embodiment, this invention relates to photographic compositions comprising a polymer which contains recurring units of the formula:

wherein D represents a polycyclic group containing a [2.2.1] bridged ring adjacent the thio atom. The polycyclic group can, of course, be substituted by various groups including additional cyclic groups, straight chain groups which preferably contain condensation groups such as esters, carbamides, urethanes and the like.

The thio-substituted compounds useful in the combinations of this invention can generally be made by reacting hydrogen sulfide, a monomercaptan or a bismercaptan with an unsaturated bridged-ring compound. Of course, intralinear groups in the case of polymers and macrocyclic compounds and external groups in the case of simple compounds, polymers and macrocyclic compounds can be present. A typical simple reaction involves the reaction of cycloalkadiene with a dienophile (i.e., having at least one double bond) by a reaction commonly known as a Diels-Alder reaction, such as those described in Organic Reactions, vol. IV, Chapters I and II, John Wiley and Sons, Inc., New York, 1948, to produce a bicyclo[2.2.1]-5-heptene. This Diels-Alder adduct is then reacted with the sulfur compound to provide a thio-substituted bicyclo[2.2.1] heptane.

Typical compounds useful in the photographic combinations of the invention contain a group generally represented by the formula:

wherein A is a methylene group, an oxygen atom, a sulfur atom or an -NH group, and is preferably a methylene group, and m is an integer of 1 to 4. The compounds can be polymeric compounds or simple compounds. When they are simple compounds they have the structure:

A A 8-10 R1 Jul- 1 group where X is O- or -NH; or R and R can groups, for example, ethylene, propylene, trimethylene, additionally be a tetramethylene, ethyleneoxyethoxyethyl, hydroxymethylethylene, ethylenethioethyl, and the like; G is selected from the group consisting of carboxymethylmethylene CH2(JH 000E carboxyethylene 10 --CH GHP and the group group, and R is a hydrogen atom, an alkyl group including substituted alkyl groups and alkyl groups containing q hetero atoms, i.e., oxygen, sulfur or nitrogen atoms, in or appended to the alkyl chain and alkyl groups termi- A A mated with an \y/ n:

w wherein m, A, and R and R individually, are as described above; and R is an alkylene, cycloalkylene or A A arylene group, which is the condensation residue of a Ag: diol or a diamine, i.e., an -O-R O-, an L \V -NHR NH an NHArNH or an group where m, A and R -R are as described above, for example, methyl, ethyl, propyl, butyl, carboxymethyl, 2,3 dicarboxynorborn-S-ylthioethoxyethoxyethyl, acetyl, propionyl, butyryl, 1,2-dicarboxyethyl, carboxypropyl, group wherein R is an alkylene, including substituted, ethoxycarbonylpropyl, methoxycarbonylethyl, 1,2 bis branched chain and hetero atom-containing alkylene (ethoxycarbonyDethyl, 2 -(norborn-2-y1)ethylthioethyl, 2- groups, including alkylene groups containing cycloalkyl- (5,6 dicarboxynorborn-Z-yl)ethylthioethyl, hydroxyproene groups therein, for example, R can be the groups:

CH: CH: NH-CH OH2NH- SCH2CHzOCHzCH OCHzCH -S pyl, hydroxyethyl, hydroxymethyl, an aryl group such and as phenyl or substituted phenyl; or the group .1 CH3 CH3 R3 Gmcmsomoms A A 0OH2/ onl-o J noon, 011103 L and Ar is an aryl group; J: rs an integer of 1 or 2 prowherein m, A and R to R are as described above. 5 vided that it is 1 when is the group;

When the compounds of the invention are polymeric, they contain recurring units having structures represented by Formula I, II, III or IV as follows:

wherein m, A, and R and R individually, are as de- 1 I scribed above, and R and R together with the carbon Wherem R f R4 are taken together wlth the carbon atom to which they are attached can be a atoms to W 10h they are attached to be a group; R is an alkylene group including substituted, branched chain, and hetero atom-containing alkylene wherein m, A, and R and R individually, and R are as described above, R is an alkylene group having 1 to 6 carbon atoms, preferably methylene; Y is an O or -NH group and R is the condensation residue of an aliphatic or aromatic dicarboxylic acid, i.e., a

HOOC- COOH III wherein A, and R and R individually, are as described above and R is an alkylene group containing an ester squ linkage, including substituted derivatives thereof, for example,

O I carboxymethylmethylene carbonyloxy (O (i- C 11-) H2 C O OH O ethyleneoxyearbonyl CH2 CH2 0 ii) O methylenecarbonyloxmethyl CH2 i l 0- 0 Hz-) carb oxymethylmethylenecarbonyloxymethyl 011-00 0 CHz-) C Hz- C O O H ethylenecarbonyloxymethyl CH OH C O 0 CH;-

trimethylenecarbonyloxymethyl -OHzCH CHzCOOCHz and the like;

wherein m, A, and R and R individually, are as described above and R and R taken together with the carbon atoms to which they are attached can be a group; R is selected from any of the groups described for R and from groups having the structure:

wherein m, A, R and R and R individually, are as described above, or when R and R are taken together with the atoms to which they are attached to form an group, R is an alkylene, arylene, arylenebisalkylene or an alkylenebisarylene, for example, phenylenedimethylene, phenylene, methylenediphenylene, ethylene, tetramethylone, and the like.

The present invention and the above formulae are also intended to include the respective sulfoxide and sulfone compounds wherein the thio atom has been oxidized to a sulfoxide or a sulfone.

The polymeric compounds of this invention can be prepared by reacting sulfur compounds such as hydrogen sulfide or mono-and/or poly-functional mercaptans with a polycyclic compound containing an unsaturated [2.2.1] bicyclic moiety. Reaction conditions favoring free radical reactions are preferred. Reactions which proceed with difficulty are catalyzed by the use of free radical catalysts such as ascaridole, peroxides and the like, or ultraviolet light, optionally with photosensitizers such as acetone, benzophenone, etc., and heat or combinations thereof. In general terms, the reaction proceeds by the addition of a mercaptan to the double bond of a [2.2.1] bicyclic moiety containing an unsaturated group. Additional functional groups such as condensable groups (i.e., alcohol, acid, amide, etc.) are generally present on the mercaptan or the polycyclic compound, especially if polymers or macrocyclic compounds are formed. The linear linkage can be completed by condensation reacting through these groups or simultaneously with the mercaptan reaction with the double bond on the [2.2.1] bicyclic moiety.

The thio-su'bstituted compounds of this invention are generally incorporated into the photographic composition by techniques generally known in the art and as described in U.S. Pat. 3,046,134. The concentration of the compounds is dependent on the particular improvement desired. In the instance of silver halide compositions, concentrations of about 0.010 mg. to about 10 g./mole of silver halide, and preferably about 0.5 mg. to about 1 g.

per mole of silver halide, are desired.

The silver halide emulsions used with this invention can comprise silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof. The emulsions may be coarse or fine grain and can be prepared by any of the well-known procedures, e.g., single-jet emulsions, double-jet emulsions such as Lippmann emulsions, ammoniacal emulsions, or thiocyanateor thioetherripened emulsions such as those described in Nietz. et al., U.S. Patent 2,222,264; lllingsworth, U.S. Patent 3,320,069; and McBride, U.S. Patent 3,271,157. Surface-image emulsions may be used or internal-image emulsions such as those described in Davey et al., U.S. Patent 2,592,250; Lowe et al., US. Patent 3,206,313; Berriman et al., U.S. Patent 3,367,778; and Bacon et al., Belgian Patent 704,255. If desried, mixtures of surfaceand internalimage emulsions may be used as described in Luckey et al., U.S. Patent 2,996,382. Negative-type emulsions may be used or direct-positive emulsions such as those described in Leermakers, U.S. Patent 2,184,013; Kendall et al., U.S. Patent 2,541,472; Berriman, U.S. Patent 3,367,778; Schouivenaars, British Patent 723,019; Illingsworth, French Patent 1,520,821; Ives, U.S. Patent 2,563,785; Knott et al., U.S. Patent 2,456,953; and Land, U.S. Patent 2,861,885.

The emulsions used with this invention may be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these. Suitable procedure are described in Shepard, U.S. Patent 1,623,499; Allen, U.S. Patent 2,399,083; McVeigh, U.S. Patent 3,297,447; and Dunn, U.S. Patent 3,297,446.

The photographic elements of this invention may contain incorporated developing agents such as hydroquinones, catechols, aminophenols, S-pyrazolidones, ascorbic acid and its derivatives, reductones and phenylenediamines. Combinations of developing agents can be employed in the practice of the invention. The developing agents can be in a silver halide emulsion and/ or in another suitable location in the photographic element. The developing agents may be added from suitable solvents or in the form of dispersions as described in Yackel, U.S. Patent 2,592,368, and Dunn et al., French Patent 1,505,778.

The photographic and other hardenable layers used in the practice of this invention can be hardened by various organic or inorganic hardeners, alone or in combination, such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfones, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed-function hardeners and polymeric hardeners such as oxidized polysaccharides such as dialdehyde starch and oxyguar gum and the like.

The photographic emulsions and elements described in the practice of this invention can contain various colloids alone or in combination as vehicles, binding agents and various layers. Suitable hydrophilic materials include both naturally occurring substances such as proteins, for example, gelatin, gelatin derivatives, cellulose derivatives; polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as water-soluble polyvinyl compounds such as poly(vinylpyrrolidone), acrylamide polymers and the like.

The described photographic emulsion layers and other layers of a photographic element employed in the practice of this invention can also contain, alone or in combination with hydrophilic, water-permeable colloids, other synthetic polymeric compounds such as dispersed vinyl compounds such as in latex form and particularly those which increase the dimensional stability of the photographic materials. Suitable synthetic polymers include those described, for example, in U.S. Patents 3,142,568 of Nottorf issued July 28, 1964; 3,193,386 of White issued July 6, 1965; 3,062,674 of Houck, Smith and Yudelson issued Nov. 6, 1962; 3,220,844 of Houck, Smith and Yudelson issued Nov. 30, 1965; 3,287,289 of Ream and Fowler issued Nov. 22, 1966; and Dykstra, U.S. Patent 3,411,911; particularly effective are those water-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, those which have crosslinking sites which facilitate hardening or curing and those having recurring sulfobetaine units as described in Canadian Patent 774,054.

The photographic layers and other layers of a photographic element employed and described herein can be coated on a wide variety of supports. Typical supports include cellulose nitrate film, cellulose ester film, poly (vinyl acetal) film, polystyrene film, po1y(ethylene terephthalate) film, polycarbonate film and related films or resinous materials, as well as glass, paper, metal and the like. Typically, a flexible support is employed, especially a paper support, which can be partially acetylated or 'coated with baryta and/or an alpha-olefin polymer, particularly a polymer of an alpha-olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.

The photographic layers employed in the practice of this invention can contain plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton, U.S. Patent 2,960,404; fatty acids or esters such as those described in U.S. Patent 2,588,765 and Duane, U.S. Patent 3,121,060; and silicone resins such as those described in Du Pont, British Patent 955,061.

The photographic layers employed in the practice of this invention may contain surfactants such as saponin, anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen, U.S. Patent 2,600,831, and amphoteric compounds such as those described in Ben-Ezra, U.S. Patent 3,133,816.

The light-sensitive silver halide emulsion of the multilayer photographic elements of the invention can conveniently be ortho-sensitized or pan-sensitized with spectral sensitizing dyes. For instance, these emulsions can be spectrally sensitized by treating with a solution of a sensitizing dye in an organic solvent or the dye may be added in the form of a dispersion as described in Owens et al., French Pat. 1,482,774. sensitizing dyes useful in sensitizing such emulsions are described, for example, in U.S. Pats. 2,526,632 of Brooker and White issued Oct. 24, 1950; 2,503,776 of Sprague issued Apr. 11, 1950; 2,493,- 748 of Brooker et al.; and 3,384,486 of Taber et al. Spectral sensitizers which can be used include the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls and hemicyanines. The cyanines may contain such basic nuclei as thiazoles, oxazoles, selenazoles or imidazoles. Such neceli may contain sulfoalkyl, carboxyalkyl and alkylamino groups and may be fused to benzene or naphthalene rings either unsubstituted or substituted with halogen, phenyl, alkyl or alkoxy groups. The dyes may be symmetrical or unsymmetrical and may contain alkyl, phenyl or heterocyclic substitutents on the polymethine chain. The merocyanine dyes may contain the basic nuclei mentioned above as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenedienes and barbituric acids. The acid nuclei may be substituted with alkyl groups, phenyl groups, carboxy groups, sulfo groups or amino groups. The emulsions may contain supersensitiling dye combinations such as those described in U.S. Pats. 2,739,964 by Brooker et al.; 2,688,545 by Carroll et al.; 2,701,198 by Carroll et al.; 2,739,149 by VanLare; and British Pat. 1,128, 840 by Fuji; or the dyes may be supersensitized with ascorbic acid derivatives, azaindenes, cadmium salts, and organic sulfonic acids as described in U.S. Pats. 2,933,390 by McFall et al. and 2,937,089 by Jones et al.

The photographic layers used in the practice of this invention may be coated by various coating procedures including dip coating, air knife coating, curtain coating or extrusion coating using hoppers of the type described in Beguin, U.S. Pat. 2,681,294. If desired, two or more layers may be coated simultaneously by the procedures described in Russell, U.S. Pat. 2,761,791, and Wynn, British Pat. 837,095.

This invention may be used with elements designed for colloid transfer processes such as described in Yackel et al., U.S. Pat. 2,716,059; silver salt dilfusion transfer processes such as described in U.S. Pats. 2,352,014 by Rott, 2,543,181 by Land, 3,020,155 by Yackel and 2,861,- 885 by Land; color-image transfer processes such as described in U.S. Pats. 3,087,817, 3,185,567 and 2,983,606 by Rogers, 3,253,915 by Weyerts, 3,227,550, 3,227,551 and 3,227,552 by Whitmore et al., and 3,415,644, 3,415,- 645 and 3,415,646 by Land; and imbibition transfer processes as described in U.S. Pat. 2,882,156 by Minsk.

This invention may be used with elements designed for color photography, for example, elements containing colorforming couplers such as those described in U.S. Pats. 2,376,679 by Frohlich et al.; 2,322,027 by Vittum et 211.; 2,801,171 by Fierke et al.; 2,698,794 by Godowsky; 3,227,554 by Barr et al.; and 3,046,129 by Graham; or elements to be developed in solutions containing colorforming couplers such as those described in U.S. Pats. 2,252,718 by Mannes and Godowsky; 2,592,243 by Carroll et a1.; and 2,950,970 by Schwan.

Typical compounds useful in the practice of the invention are listed below or, in the instance of polymeric or macrocyclic compounds, they contain units as represented below wherein n is a positive integer.

Sample number Structure S-CH CH O CH CH S S OHmH O -OH CHzS COOH COOH

S-CH CH 0-CH on s H000 2 /1 2 2 HOOC S CHzCHzO -CHgCHg S H000 a 2 2 coon OOOH TABLEContinued Sample number Structure 52.....'..'.. CH: CH;

O E i OH L U.

ll II C C O /O C C I! I! O O 54 (I? o S N CH1 0 HgN i! 0 O u 03:00 S G-OCHI HO O C C O OH HO O C- S C O 0 H H0 0 C C O OH HO C H: C H: OH

This invention is further illustrated by the following examples. Additional examples of preparation of compounds of this type are disclosed in copending application U.S. Ser. No. 880,896, filed on even date herewith.

PREPARATION OF COMPOUNDS Example l.--Sample 9: Copoly[hicyclo[2.2.l] 5 heptene 2,3 dicarboxylic anhydride-bis(Z-mercaptdthyl) -su1fide-hexamethylene diamine] Bicyclo[2.2.1]-5-heptene 2,3-dicarboxy1ic anhydride, 32.8 grams (0.2 mole), is dissolved in 100 ml. of be rijzene and mixed with 15.4 grams (0.1 mole) of bis(2-mer"captoethyl)sulfide. After 2 days, /2 of the benzene solution is stirred with an aqueous solution of 5.8 grams (0.05 iiiole) of distilled hexarnethylene diamine and 0.1 mole of sodium hydroxide in 50 ml. of water. The mixture is heated to 80 (3., left standing overnight at room temperattire, mixed with ethyl acetate and extracted with water. The aqueous layer is acidified with dilute hydrochloric acid to give a white stringy polymer which is purified by three more precipitations from aqueous solutions of its sodium salt with acid followed by washing with water after each precipitation.

Analysis.-Calculated for C H N 0 S (percent): C, 56.7; H, 6.1; N, 4.7; S, 16.2; [N.E.], 296. Found (percent): C, 53.0; H, 7.2; N, 4.1; S, 15.3; [N.E.}, 284.

Example 2.-Sample 14: Copoly[1,2 bis(2 mercaptoethoxy)ethane-dodecahydro 1,4:5,8 dimethaiioanthraquinonylene-2,6 (or 7)] 1,4,4a,5,8,8a,9a,10a octahydro 1,4:5,8 dimethano- 9,10-anthraquinone, 12 grams (0.05 mole), and 1,2-bis (2-mercaptoethoxy)ethane, 9.1 grams (0.05 mole), are

mixed with 4 drops of ascaridole, the temperature rising spontaneously from 24 C. to 32 C. in 2 minutes. The reaction mixture is then heated for 24 hours and precipitated from benzene with methanol.

Analysis.-Calculated (percent): C, 62.5; H, 7.1; S, 15.1. Found (percent): C, 61.0; H, 7.1; S, 14.9; MW, 460.

Example 3.-Sample l9: S-carboxymethylmercaptobicyclo [2.2. 1 heptene-2,3-dicarboximide tBicyclo[2.2.l] 5 heptene 2,3 dicarboximide, 8.7 grams (0.053 mole), and 19.5 grams (0.21 mole) mercaptoacetic acid are mixed with 4 drops of ascaridole and heated for 1 hour on the steam bath. Two more drops of ascaridole are added and the heating is continued for an additional 10 hours. The crystals which form are washed with benzene and recrystallized from ethyl acetate. Melting point: 151-152 C.

Analysis.-Calcu1ated for C I-1 N0 8 (percent): C, 51.7; H, 5.10; N, 5.50; S, 12.5. Found (percent): C, 61.3; H,-5.3; N, 5.3; S, 12.2.

Example 4.Sample 38 5.5 (or 5,6) thiobis(bicyclo{-2.2.1lheptane 2,3-dicarboxylic acid anhydride), 9.62 grams (0.0265 mole), is dissolved in 500 ml. of glacial acetic acid and 6 m1. of 32 percent aqueous hydrogen peroxide is added. The reaction mixture is allowed to stand for 48 hours at room temperature. The solution is heated for 1 hour on a steam bath, the solvent is removed and the residue is taken up in hot ethyl acetate. Benzene is added to produce a cloud point and, after standing for several weeks, 10 grams of white crystals separate. Melting point 310 C. Analysis indicates that the product is the tetrabasic acid. After drying overnight under vacuum at C., the anhydride is formed in quantitative yield.

21 Example 5.-Sample 41 Equimolar amounts of mercaptosuccinic acid and bicyclo[2.2.1]-2-methyl 3,3-dihydroxymethylS-heptene are mixed at room temperature in an inert atmosphere of nitrogen. After the initial exothermic reaction subsides, a small quantity (2-4 drops) of ascaridole is added. The reaction mixture is heated for several hours at 21 mm. Hg in the presence of an esterification catalyst. Upon completion of the reaction and cooling to room temperature, a hard, glassy solid forms.

Analysis.Calculated for C H SO (percent): C, 56.0; H, 6.67; S, 10.65. Found (percent): C, 55.2; H, 6.7; S, 10.7.

Example 6.-Sample 45 A mixture of 3 methylbicyclo[2.2.1]-5-l1eptene-2-ylmethyl 3 methylbicyclo[2.2.1]-5-heptene-2-carboxylate, 68 grams (0.25 mole), and benzophenone, 0.375 gram (0.00206 mole), are dissolved in 375 ml. of cyclohexane in a 500-ml. quartz fiask equipped with a magnetic stirrer, a sintered glass bubbling tube and an outlet tube. The reaction mixture is stirred while hydrogen sulfide gas is bubbled into the solution. The flask is irradiated with a 275-watt sun lamp placed 1 inch from the outer surface of the flask. After 70 hours of reaction, the hot solution (68 C.) is allowed to cool to room temperature and an insoluble oil settles out.

The oil is dissolved in 100 ml. of ethyl acetate, precipitated in 700 ml. of ethyl alcohol, dissolved in 200 ml. of methylene chloride and precipitated twice in 600 ml. of acetone. The product is then dried in a vacuum oven at 117 C. for 1 hour to yield 50 grams (65% yield) of a brittle, glassy polymer.

Example 7.Sample 51 A mixture of 4,4 methylenedianiline, 4.955 grams (0.025 mole), and dry dimethyl acetamide, 94 ml. (distilled from phosphorus pentoxide), is placed in a flamed 250-ml. flask equipped with a nitrogen tube, magnetic stirrer and drying tube. 5,5 (or 5,6) thiobis(bicyclo [2.2.1]heptene-2,3 dicarboxylic acid anhydride), 9.06 grams (0.025 mole), is added with stirring to the above mixture. The reaction mixture is stirred under nitrogen for 17 hours and then stored in a freezer.

The reaction mixture is placed on a glass plate, heated under nitrogen for 20 minutes at 80 0., held at 400 microns of Hg for 1 hour at 25 C. and then held under nitrogen for 1 hour at 300 C. The resulting polymer is a clear, hard resin.

The same compound can be prepared by reacting the half-ester (dimethyl) of the bisanhydride above with 4,4- methylenedianiline.

Example 8.-Sample 56 5,5'( or 5,6) thiobis(bicyclo[2.2.1]heptane- 2,3-dicarboxylic acid anhydride) is hydrolyzed with 4 parts of sodium hydroxide in water and then acidified with dilute hydrochloric acid. The product is the tetrabasic acid shown above.

Example 9 Samples of the compounds listed above are added to a coarse-grained silver bromoiodide emulsion which contains 6.25 mole percent iodide and which is panchromatically sensitized with a cyanine dye. The emulsion samples are coated on a cellulose acetate support at a coverage of 459 mg. of silver and 1040 mg. of gelatin per square foot. Samples of the coatings are exposed on an Eastman 1B sensitometer, processed for 5 minutes in Kodak Developer DK-50, fixed, washed and dried.

Results of tests run on sample coatings are set forth in Table l.

TABLE 1 Incubation at 120 Fresh test F., 50% RH Concentration, Rela- Rela- N0. Sample g. [mole tive tive of 0. Ag speed 7 Fog speed 1 Fog week Example 10 Some of the coatings of Example 9 containing the compounds listed above are given forced development, i.e., development for 12 minutes in Kodak Developer DK-SO, which is a longer development than is usually given, in

23 order to elicit any fogging tendencies of the compound. Sensitometric results given in Table 2 below show substantial lowering of fog in coatings conatining the compounds of the invention.

TABLE 2 Forced development Concentration, Relgi/mole ative Sample No. Ag speed 7 Fog Although the invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, variations and modifications can be cifected within the spirit and scope of the invention.

We claim:

1. A silver halide photographic composition containing an antifogging concentration therein of (1) a simple compound having the structure:

group where X is -0- or -NH, or a 24 group; and R is a hydrogen atom, an alkyl group, an aryl group, or the group:

q x R. Y

wherein A, m, R R R and R are as described above; or (2) a polymeric compound consisting essentially of recurring units with structures selected from:

L wherein m, A, and R and R taken individually are as described above or R and R taken together with the carbon atoms to which they are attached form a group; R is an alkylene group; G is a carboxymethylmethylene group, a carboxyethylene group, or a group having the structure:

wherein R and R are taken together with the carbon atoms to which they are attached to form a group;

wherein m, A, and R and R taken individually are as described above; R is an alkylene group having 1 to 6 carbon atoms; Y is an O- or NH- group; and R is the condensation residue of a dicarboxylic acid;

III

wnerein A, and R and R taken individually are as described above; and R is an alkylene group containing an ester or amido linkage; and

. aw r l/ W wherein m, A, and R and R taken individually are as described above, and R and R when taken together with the carbon atoms to which they are attached are a 0 ll N o ll group; R is selected from any of the groups described for R1 and from groups having the structure:

W a: i 3&1} 522- wherein m, A, R and R and R taken individually, are as described above, or when R and R are taken together with the atoms to which they are attached to form a RD Y Rl0 5. The photographic silver halide emulsion of claim 1 containing the compound 5,5(or 5,6')-sulfonylbis (bicycle-[2.2.1]heptane-2,3-dicarboxylic acid anhydride).

6. A photographic composition according to claim 1 wherein said compound is the polymeric condensation product of 1,8-bis(2,3-oxydicarbonylnorborn-S-ylthio)- 3,6-dioxaoctane; 1-( l,2-oxydicarbonylethylthio-8- (2,3-dicarboxynorborn-S-ylthio) )-3,6-dioxaoctane; 1,8 bis(1,2- oxydicarbonylethylthio)-3,6-dioxaoctane; and 1,6-hexylenediamine.

7. A photographic composition according to claim 1 wherein said compound is the polymeric condensation product of 1,8-bis(2,3 oxydicarbonylnorborn-S-ylthio)- 3,6-dioxaoctane and piperazine.

8. A photographic composition according to claim 1 wherein said compound is the polymeric condensation product of 1,8-bis(2,3-oxydicarbonyl 7 oxabicyclo [2.2.1]hept-S-ylthio)-3,6-dioxaoctane and 1,6-hexylenediamine.

9. A photographic composition according to claim 1 wherein said compound is 1,8-bis(2,3-dicarboxynorborn- S-ylthio)-3,6-dioxaoctane.

10. A photographic composition according to claim 1 wherein said compound is 2-carboxymethylthionorbornane.

11. A photographic composition according to claim 1 wherein said compound is 2,5(6)-dimercaptonorbornane.

12. A photographic composition according to claim 1 wherein said compound is 2,6(7)dimercapto-1,4:5,8-dimethanoperhydronaphthalene.

13. A photographic composition according to claim 1 wherein said compound is 2-hydroxymethyl-5 (6)-mercaptonorbornane.

14. A photographic composition according to claim 1 wherein said compound is poly[2-(1,2-dicarboxyethylthio -5 (6) -hydroxymethylnorbornane] 15. A photographic composition according to claim 1 wherein said compound is poly[2-carboxy-3-methyl-5(6)- (Z-hydroxymethyl 3 methylnorborn-5-(6)-ylthio)norbornane.

16. A photographic composition according to claim 1 wherein said compound is poly[2,2-bis(hydroxymethyl)- 3-methyl-5(6)-(1,2-dicarboxyethylthio)no rbornane.

17. A photographic composition according to claim 1 wherein said compound is S-actylthionadic anhydride.

18. A photographic composition according to claim 1 wherein said compound is 2,5(6)-bis(acetylthio)norbornane.

19. A photographic composition according to claim 1 wherein said compound is 2,6(7)-bis(acetylthio)-l,4:5, 8, :9 ,10-trimethanoperhydroanthracene.

20. The photographic silver halide emulsion of claim 1 containing the compound copoly[bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic anhydride-hexamethylene diaminebis 2-mercaptoethoxy) ethane] 21. The photographic silver halide emulsion of claim 1 containing the compound copoly[bicyclo[2.2.l]-5-heptene-2,3-dicarboxylic anhydride-ethylene diamine-bis(2- mercaptoethoxy) ethane] 22. The photographic silver halide emulsion of claim 1 containing the compound copoly[bicyclo[2.2.l] 5 heptene 2,3-dicarboxylic anhydride-hexamethylene diaminebis 1,2-mercapto propanol] 23. The photographic silver halide emulsion of claim 1 containing the compound copoly[bicyclo[2.2.l] 5 hep- 27 tene-2,3-dicarboxylic anhydride-Z-methyl 2 aminomethylbicyclo--heptene-bis-(Z-mercaptoethoxy)ethane].

24. The photographic silver halide emulsion of claim 1 containing the compound 2,6(or 7)di(carboxymethylmercapto) dodecahydro-1,4: 5 ,8-dimethanoanthraquinone.

25. The photographic silver halide composition of claim 1 containing the polymeric compound having the formula:

wherein n is a positive integer.

26. The photographic silver halide composition of claim 1 containing the polymeric compound having the formula:

wherein n is a positive integer.

27. The photographic sliver halide composition of claim 1 containing the polymeric compound having the formula:

l 3H: on, Sl 101 0 1 wherein it is a positive integer.

28. The photographic silver halide emulsion of claim 1 containing the compound 5,5'-(or 5,6')-thiobis[bicyclo- [2.2.11-S-heptane-2,3-dicarboxylic acid].

29. A silver halide photographic composition according to claim 1 wherein said compound is a polymeric compound having recurring units of the structure:

Jm-i wherein m is an integer from 1 to 4, A is methylene group, an oxygen atom, a sulfur atom or an NH group, R and R when taken individually are each a hydrogen atom, an alkyl, carboxy, mercapto, cyano, acylthio, or an alkanol group, or R and R taken together with the carbon atoms to which they art attached form a group, R is an alkylene group, G is a carboxymethylene group, a carboxyethylene group, or a group having the structure Jul-l 28 where m, A, R and R taken individually are as described above, R is an alkylene, cycloalkylene or arylene group which is the condensation residue of a diol or a diamine, and x is an integer of 1 or 2 and must be 1 only when G is the group:

wherein R and R are taken together with the carbon atoms to which they attached to form a 30. A photographic composition according to claim 29 wherein said compound is the polymeric condensation product of 1,8-bis (2,3 oxydicarbonylnorborn-Sylthio)- S-thiopentane and 1,6hexylenediamine.

31. A photographic composition according to claim 29 wherein said compound is the polymeric condensation product of 1,8-bis(2,33oxydicarbonylnorborn-5-ylthio)- 3,6-dioxaoctane and 1,6-hexylenediamine.

32. A photographic composition according to claim 29 wherein said compound is the polymeric condensation product of 1,8-bis(2,33oxydicarbonylnorborn-S-ylthio)- 3,6-dioxaoctane and 1,2-ethylenediamine.

33. A photographic composition according to claim 29 wherein said compound is the polymeric condensation product of 1,2-bis(2,3-oxydicarbonylnorborn-S-ylthio)2- hydroxyriiethylethane and 1,6-hexylenediamine.

34. A photographic composition according to claim 29 wherein said compound is the polymeric condensation product of 1,8-bis(2,3ovydicarbonylnorborn-S-ylthio)- 3,6-dioxaoctane and l,8 bis(aminomethyl-Z-methylnorhorn-5 (6 ylthio) -3,6-dioxaoctane.

35. A photographic composition according to claim 29 wherein said compound is copoly[1,2-bis(2-mercaptoethoxy)ethanedodecahydro 1,4:5,8 dimethanoanthraquinonylene-2,6(7)

References Cited UNITED STATES PATENTS 3,411,913 11/1968 Faber et al 96-109 X 3,008,829 11/1961 Clementi et al. 96-109 X 3,043,697 7/ 1962 Forsgard 96-109 3,544,327 12/ 1970 Abel 96-109 3,459,549 8/1969 McBride et al. 96-109 X NORMAN G. TORCHIN, Primary Examiner W. H. LOUIE, JR., Assistant Examiner US. Cl. X.R. 

